Corrosion resistant coatings containing an amorphous phase

ABSTRACT

An amorphous mineralized coating upon an iron containing surface wherein the amorphous mineralized coating has a formula AxByOz-nH2O wherein A comprises iron and B comprises silicon and the values of x, y and z are greater than zero; wherein the amorphous mineralized coating comprises an amorphous phase and inorganic complex oxide crystals.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation in part of U.S. patent application Ser. No. 08/791,337 filed on Jan. 31, 1997, now U.S. Pat. No. 5,938,976, and Ser. No. 08/634,215, abandoned, entitled "Corrosion Resistant buffer System for Metal Products" and filed on Apr. 18, 1996 in the names of Robert L. Heimann, et al., which is a continuation in part of U.S. patent application Ser. No. 08/476,271 filed on Jun. 7, 1995, abandoned, which in turn is a continuation-in-part of U.S. patent application Ser. No. 08/327,438 filed on Oct. 21, 1994, now U.S. Pat. No. 5,714,093; the disclosure of each of the previously identified patent applications is hereby incorporated by reference.

FIELD OF THE INVENTION

The instant invention relates to the forning coatings on metal containing surfaces and to methods of forming such coatings on a suitable substrate. The coating can include a wide range of compounds and normally at least a portion of the coating corresponds to an amorphous phase. The inventive coating and method are particularly useful in providing a corrosion resistant coating or film upon a metallic surface. This aspect of the invention involves the formation of a corrosion resistant "mineralized" layer of tailored composition upon a metal containing surfaces.

BACKGROUND OF THE INVENTION

The corrosion of steel and other metal containing products continues to be a serious technical problem which has profound effects on the economy. Corrosion causes loss of natural resources, and deteriorates key infrastructure such as roads and buildings. It also causes premature replacement of equipment and parts in industrial facilities, boats and other marine vehicles, automobiles, aircraft, among a wide range of metallic components.

Current industry standards for corrosion prevention center around the use of barrier coatings, sacrificial coatings, alloys containing heavy metals such as chromium, nickel, lead, cadmium, copper, mercury, barium, among other heavy metals. The introduction of these materials into the environment, however, can lead to serious health consequences as well as substantial costs to contain or separate the materials or clean up environmental contamination. Damage associated with corrosion, accordingly, is a continuing problem and better systems for preventing corrosion are still needed.

A more detailed discussion of mineral containing materials can be found in Manual of Mineralogy, by Dana, 21^(st) edition, American Society of Metals, vol. 13, Corrosion in Structures, "Reaction Sequence in Atmospheric Corrosion of Zinc ASTM STP 1239", by W. W. Kirk et al., and Physics and Chemistry of Mineral Surfaces, by Bradly (1996); the disclosure of each of the aforementioned references is hereby incorporated by reference.

Conventional practices for improving protecting metal containing surfaces and imparting improved surface characteristics to metals rely upon compositions and methods which are undesirable as being costly or environmentally unsound.

SUMMARY OF THE INVENTION

The instant invention solves problems associated with conventional practices by providing an improved method and a composition for improving the surface characteristics of a metal containing surface. While the inventive composition is normally compatible with conventional compositions and methods, the inventive composition can obviate the need to employ heavy metals such as chrome and environmentally undesirable solvents.

The present invention in a broad aspect relates to compositions and methods for improving or modifying the surface characteristics of a metal containing surface. In one aspect, the invention involves methods for forming a "mineralized" layer upon the surface of a substrate. One method of forming the mineralized layer comprises delivering precursors of the mineralized layer to the surface of the metal surface via a carrier. The carrier can be a wide range of known compositions such as a film forming composition, lubricants, gel, sealant, adhesive, paint, solvent and water-borne resins, among other conventional compositions for forming coatings or films upon metals. If desired, the carrier can function as a reservoir of precursor materials thereby permitting additional formation of the mineralized layer, e.g., when in the presence of a reservoir a breach in the mineralized layer can be overcome by secondary mineral formation from mineral precursors in the reservoir--a so-called self healing effect. If desired, the carrier can also function as a reservoir of buffer materials, e.g., materials that passivate the pH of the metal surface, which can protect the metal surface by providing an environment in which the metal is resistant to chemical attack. Depending upon the utility of the carrier, the carrier can be removed or remain permanently in contact with the mineralized surface (and at least a portion of the metal surface).

The instant invention provides an improved surface on articles by tailoring the surface chemistry and effecting a new mineralized surface through chemical reaction and interaction. The mineralized surface is formed when precursors are delivered to the surface of a metal or metal coated articles or substrates. In some cases, the carrier includes materials which can function to buffer the surface, as a precursor of the mineralized layer, alter pH, activate the surface by changing the surface chemical species, or all of these functions. In some cases, the surface mineralization is enhanced by a pretreatment step prior to application of the precursor containing carrier. After providing a proper environment, precursors can interact thereby in situ forming the mineralized layer upon at least a portion of the metal surface. Depending upon the surface environment, the metal or metal coated substrate can contribute donor ions to react and/or interact with delivered precursors thereby forming a relatively thin mineralized layer that is effective in altering and preferably enhance the characteristics of the entire article, e.g., by altering and preferably enhancing the surface characteristics of the article. Consequently, the instant invention permits tailoring a metal containing surface to possess improved corrosion, coating adhesion, chemical resistance, thermal resistance, mechanical abrasion, acid rain resistance, UV resistance, resistance to effects from atomic oxygen and vacuum UV, engineered electrical resistance, among other improved properties. As will be described below in greater detail, at least a portion of the mineralized coating or layer normally corresponds to a novel amorphous phase.

DETAILED DESCRIPTION

The instant invention relates to compositions and methods for forming a mineralized coating or film upon at least a portion of a metal containing surface. By "mineralized" it is meant a composition containing at least one member selected from the group of oxygenated cations and anions wherein at least a portion of the mineralized composition corresponds to an amorphous phase, an inorganic complex oxide crystal and mixtures thereof. Normally, the amorphous phase is the predominate phase component of the mineralized layer and substantially transparent to visible light. This type of predominately amorphous phase is characterized by a continuous random network (CRN). In general, the mineral layer can possess a network structure in which metal atoms are bound to oxygen atoms by predominantly covalent bonds. The CRN can be modified by introducing metal oxides which are, in many embodiments of the invention, contributed by the substrate.

By "metal containing surface", "substrate", or "surface" it is meant to refer to a metallic article and any metal containing surface as well as any substrate at least partially coated with a metal layer, film or foil including a non-metallic article having a metal layer. A wide variety of substances can be employed as precursors of the mineralized layer, such as one or more cations of the metals of Groups I, II and III, and the transition metals, of the Periodic Chart of the Elements. Additionally, the mineralized layer can comprise one or more of the anions selected from the group consisting of water soluble salts and/or oxides of tungsten, molybdenum, chromium, titanium, zircon, vanadium, phosphorus, aluminum, iron, boron, bismuth, gallium, tellurium, germanium, antimony, niobium (also known as columbium), magnesium and manganese, mixtures thereof, among others. Particularly, desirable results have been achieved by employing salts and oxides of silicon, aluminum and iron.

At least a portion of the resulting mineralized layer having CRN attributes comprises:

    A.sub.x B.sub.y O.sub.z --nH.sub.2 O

where A is termed a modifier cation and may be one or more ions of Group I, II and/or III metals, and B is a network forning cation, such as silicon. The values of x and y can be any number including zero but x and y cannot all concurrently be zero and z cannot be zero. The relationships of x, y, and z follow rules by Zachariasen in the Journal of the American Chemical Society, Volume 54, page 3841 (1932); hereby incorporated by reference:

1. A high proportion of (network-forming) cations are surrounded by oxygen tetrahedra or triangles,

2. The oxygen polyhedra only share comers with each other; and,

3. Some oxygen atoms are linked to only two cations, and do not form additional bonds with any other cations.

The mineralized layer is formed from precursors. By "precursors" it is meant any combination of materials which interact to form the mineralized layer as well as intermediate products that interact further to form the mineralized layer. Examples of precursors include buffers such as silicate buffers and carbonate buffers including sodium hydroxide; silicates such as at least one of sodium, calcium and potassium silicate; silica; cations supplied or delivered to the surface such as at least one of zinc, molybdenium; ions supplied or delivered to the surface such as at least one of oxygen, sulfir or chlorine from the environment surrounding the precursors or surface; compounds which decompose or react to form a precursor or intermediate thereof; mixtures thereof, among others. The mineralized layer can be tailored by adding one or more dopants to the precursor. Examples of suitable dopants comprise at least one member from the group consisting of anions selected from the group consisting of water soluble salts and/or oxides of tungsten, molybdenum, chromium, titanium, zircon, vanadium, phosphorus, aluminum, iron, boron, bismuth, gallium, tellurium, germanium, antimony, niobium (also known as columbium), magnesium and manganese, mixtures thereof, among others, and more especially, salts and oxides of aluminum and iron. Desirable results can be obtained by adding one or more dopants to a sodium silicate precursor.

The precursors of the mineralized layer are added to any suitable carrier. Examples of suitable carriers include hydrocarbons such as at least one member selected from the group consisting of animal, vegetable, petroleum derived and synthetic oils such as polyalphaolefin (PAO), silicone oil, phosphate esters, fluorinated oils such as KRYTOX (supplied by the DuPont Company). Further examples of suitable carriers comprise at least one member selected from the group consisting of thermoplastic, thermosetting, cross-linked system, mixtures thereof, among others. Specific examples of such carriers include epoxies, acrylics, polyurethanes, silicones, polyesters, alkyds, vinyls, phenolics, fluoropolymers, latexes, mixtures thereof, among others. Depending upon the process conditions, the precursor carrier may be selected from alkylated aromatics, phosphate esters, perfluoroalkylpolyethers, polyesters, olefins, chlorotrifluoroethylene, silahydrocarbons, phosphazenes, dialkylcarbonates, oligomers, polybutenes, and polyphenyl esters, as well as unsaturated polyglycols, silicones, silicate esters, cycloaliphatic hydrocarbons, and dibasic acid esters, e.g., when applying a precursor carrier to an iron containing surface a polyalphaolefin base oil having a kinematic viscosity in the range of about 30-1,400 centistokes at 40° C. can be employed. Other properties to consider when choosing an appropriate polyalphaolefin base oil are molecular weight, molecular branching, thermal stability, and hydrophobicity, depending on the application. The polyalphaolefin base oil can be thickened to a gel with thickeners known to the art of grease manufacturers such as polytetrafluoroethylene or silica Buffer materials are also suitable as thickeners as long as they are compatible with the base oil. Generally, low molecular weight, synthetic, hydrocarbon oils provide greater ease in designing and manufacturing a gel with particular desired characteristics but are more costly than less refined, high molecular weight, petroleum hydrocarbon oils. Less refined hydrocarbons may also have the disadvantage of containing sulfide compounds which can feed sulfate reducing bacteria and, in turn, tend to corrode metals such as steel, iron and iron alloys.

The carrier film or layer can have a thickness of about 1 to at least about 50 mils, and typically has a thickness of about 1 to about 1.5 mil, e.g., about 0.2 to at least 0.4 mil. Normally, the carrier is semipermeable thereby permitting anions from the surrounding environment to contact precursors to the mineralized product. By "semipermeable" it is meant to refer to a microporous structure, either natural or synthetic allowing passage of ions, water and other solvent molecules, and very small other molecules. The resin can be essentially insoluble in water and resistant to macro-penetration by flowing water. The resin layers, however, are normally permeable to water molecules and inorganic ions such as metal ions and silicate ions.

The amount of mineralized layer precursor present in the carrier typically comprises about 1 to about 60 wt. % of the carrier, e.g., normally about 5 to about 10 wt. % depending upon the carrier. The mineralized layer precursors can be combined with the carrier in any suitable conventional manner known in this art.

The mineralized layer precursors can include or be employed along with one or more additives such as the pH buffers such as those listed below in Tables A and B, mixtures thereof, among others. In some cases, a buffer also functions as a precursor, e.g., sodium silicate. The amount of these additives typically ranges from about 1 to about 60 wt. % of the carrier, e.g., normally about 5 to about 10 wt. %. These additives can be added to the carrier in order to tailor the characteristics of the mineralized layer, the carrier itself, upon a pre-treated surface, among other characteristics. By adding suitable mineralized layer precursors, carrier, additives, among other materials, the surface of the metal containing layer can be tailored by forming a mineralized layer to possess improved corrosion resistance, adhesion, among other characteristics.

                  TABLE A                                                          ______________________________________                                         Examples of Buffering Compounds                                                Chemical Name     Formula                                                      ______________________________________                                         Boric Acid        H.sub.3 BO.sub.3                                             Citric Acid       H.sub.3 C.sub.6 H.sub.5 O.sub.7.H.sub.2 O                    Sodium Hydroxide  NaOH                                                         Trisodium Phosphate                                                                              Na.sub.3 PO.sub.4.12H.sub.2 O                                Dodecahydrate                                                                  Potassium Silicate                                                                               SiO.sub.2 /K.sub.2 O 1.6-2.5 wt. ratio                       Sodium Silicate   SiO.sub.2 /Na.sub.2 O 2.0-3.22 wt. ratio                     Potassium Hydrogen                                                                               KHC.sub.8 O.sub.4 H.sub.4                                    Phthalate                                                                      Potassium Dihydrogen                                                                             KH.sub.2 PO.sub.4                                            Phosphate                                                                      Borax             Na.sub.2 B.sub.4 O.sub.7                                     Sodium Hydrogen Carbonate                                                                        NaHCO.sub.3                                                  Disodium Phosphate                                                                               Na.sub.2 HPO.sub.4.12H.sub.2 O                               Dodecahydrate                                                                  Sodium Acetate    NaOOCCH.sub.3                                                Disodium Phosphate                                                                               Na.sub.2 HPO.sub.4                                           ______________________________________                                    

                                      TABLE B                                      __________________________________________________________________________     Examples of Weight Ratios of Buffering Components for Various pH Values        Desired                                                                        pH   Weight                                                                             Chemical                                                                              Weight                                                                             Chemical                                                                              Weight                                                                               Chemical                                      __________________________________________________________________________     3.0  1.00                                                                               Boric Acid                                                                             0.84                                                                              Citric Acid                                                                            0.18 Trisodium                                                                      Phosphate                                     3.5  1.00                                                                               Boric Acid                                                                             0.84                                                                              Citric Acid                                                                             .027                                                                               Trisodium                                                                      Phosphate                                     4.0  1.00                                                                               Sodium 196.00                                                                             Potassium                                                                             Hydrogen                                                                             Phthalate                                              Hydroxide                                                             4.5  1.00                                                                               Sodium 29.30                                                                              Potassium                                                                             Hydrogen                                                                             Phthalate                                              Hydroxide                                                             5.0  1.00                                                                               Sodium 11.30                                                                              Potassium                                                                             Hydrogen                                                                             Phthalate                                              Hydroxide                                                             5.5  1.00                                                                               Sodium  6.97                                                                              Potassium                                                                             Hydrogen                                                                             Phthalate                                              Hydroxide                                                             6.0  1.00                                                                               Sodium 30.40                                                                              Potassium                                                                             Dihydrogen                                                                           Phosphate                                              Hydroxide                                                             6.5  1.00                                                                               Sodium 12.20                                                                              Potassium                                                                             Dihydrogen                                                                           Phosphate                                              Hydroxide                                                             7.0  1.00                                                                               Sodium  5.84                                                                              Potassium                                                                             Dihydrogen                                                                           Phosphate                                              Hydroxide                                                             7.5  1.00                                                                               Sodium  4.14                                                                              Potassium                                                                             Dihydrogen                                                                           Phosphate                                              Hydroxide                                                             8.0  1.00                                                                               Sodium  3.64                                                                              Potassium                                                                             Dihydrogen                                                                           Phosphate                                              Hydroxide                                                             8.5  1.00                                                                               Boric Acid                                                                             0.84                                                                              Citric Acid                                                                           4.80  Trisodium                                                                      Phosphate                                                                      (12H.sub.2 O)                                 9.0  1.00                                                                               Boric Acid                                                                             0.84                                                                              Citric Acid                                                                           5.82  Trisodium                                                                      Phosphate                                                                      (12H.sub.2 O)                                 9.5  1.00                                                                               Sodium 13.55                                                                              Borax                                                               Hydroxide                                                             10.0 1.00                                                                               Sodium  6.52                                                                              Borax                                                               Hydroxide                                                             10.5 1.00                                                                               Sodium  5.25                                                                              Borax                                                               Hydroxide                                                             11.0 1.00                                                                               Sodium  2.31                                                                              Sodium Hydrogen                                                                             Carbonate                                              Hydroxide                                                             11.5 1.00                                                                               Sodium  8.00                                                                              Disodium                                                                              Acid Phosphate (12H.sub.2 O)                                 Hydroxide                                                             12.0 1.00                                                                               Sodium  1.30                                                                              Disodium                                                                              Acid Phosphate (12H.sub.2 O)                                 Hydroxide                                                             12.5 1.00                                                                               Sodium 15.00                                                                              Disodium                                                                              Acid Phosphate                                               Hydroxide                                                             13.0 1.00                                                                               Sodium  1.00                                                                              Sodium Acetate                                                      Hydroxide                                                             __________________________________________________________________________

The aforementioned carrier can be applied to a metal containing surface by using any expedient method. Depending upon the desired results, the a carrier containing a mineralized layer precursor can be applied or reapplied as appropriate. Examples of suitable methods for applying the tailored carrier comprise at least one of painting, spraying, dipping, troweling, among other conventional methods.

By employing a suitable tailored carrier, the instant invention can form a mineralized layer to protect a metal containing surface having at least one member from the group of magnesium, aluminum, vanadium, calcium, beryllium, manganese, cobalt, nickel, copper, lead, copper, brass, bronze, zirconium, thallium, chromium, zinc, alloys thereof, among others. Particularly, desirable results can be obtained when forming a mineralized layer upon a zinc containing surface.

Without wishing to be bound by any theory or explanation, it is believed that the mineralized layer is formed under a variety of chemical and physical forces including 1) transporting ions through the carrier via osmotic pressure and diffusion thereby providing ions to the metal surface, 2) oxygen deprived environment, 3) buffering to provide a predetermined alkaline pH environment that is effective for formation of the mineralized layer upon a given metal surface, e.g., in the case of a zinc containing surface about 9.5 to at least about 10.5 pH, 4) heterogenious process using any available ions, 5) water present at the surface, in the carrier or as a reaction product can be removed via heat, vacuum or solvent extraction, 6) using a reservoir adjacent to the metal surface that can control that ion transport rate as well as the rate of water (and moieties) passing through the reservoir and serve to provide, as needed, a continuous supply mineralized layer precursors, among other forces.

The process for forming the inventive mineralized layer can be initiated by delivering buffering ions of combinations or single component alkali metal polyoxylates (for example sodium silicate) to passivate the metal surface, e.g., refer to item 3) in the previous paragraph. In the case of sodium silicate, the carrier contains dissolved silica in the form of a silicate anion in water as well as sodium oxide in the form of sodium hydroxide in the presence of water. If desired, sodium hydroxide can be employed maintaining the pH of the solution in a range where the silicate can remain soluble. In the case of other substrates and other anion systems, the buffering capacity of the reactants is designed to passivate the surface, manage the pH of the surface chemistry, activate the surface, oxidize the surface, or to prepare or condition the surface for a mineral-forming reaction or any combination of the above. The delivery of ions is through a carrier comprising a membrane employing osmotic pressure to drive precursors to the surface.

The ionic species, which are present in the carrier or that pass through the carrier/membrane, can then interact chemically and can become associated with the surface of the metal to form a submicron mineralization layer, e.g., a monolayer. In the present invention these interactions occur adjacent to or upon the surface of the substrate to form a mineralized layer. It is to be understood that the aforementioned membrane is associated with creating an oxygen-limited passivation environment as part of the mineralization process.

Moreover, the mineralized layer precursors can interact in such a manner to produce mineralized layer in-situ at the surface. Depending upon the conditions of the surface, the substrate may contribute precursors in the form of metal ions. The metal ions of the substrate surface may exist as oxides, or the ions may have reacted with chemical species in the surrounding environment to form other metal species. In the case of a zinc substrate or surface, zinc can oxidize in the environment existing at the surface as zinc oxide, but may also form zinc carbonate from the exposure to carbon dioxide in the air. Under certain conditions, the zinc carbonate will predominate the surface species of the precursor to form the mineralized surface. In the case of other metal substrates, the ability of the surface to contribute ions to function as mineral precursors can be achieved by conditioning the surface, e.g., to populate the surface with oxide species that will participate as mineralized layer precursors.

To enhance mineral layer formation on at least a portion of the surface of a metal substrate, the metal surface may be prepared or pretreated. Metal surfaces normally tend to be covered with a heterogeneous layer of oxides and other impurities. This covering can hinder the effectiveness of the buffering and/or mineral layer formation. Thus, it becomes useful to convert the substrate surface to a homogenous state thereby permitting more complete and uniform mineral layer formation. Surface preparation can be accomplished using an acid bath to dissolve the oxide layers as well as wash away certain impurities. The use of organic solvents and detergents or surfactants can also aid in this surface preparation process. Phosphoric acid based cleaners, such as Metal Prep 79 (Parker Amchem), fall into a category as an example commonly used in industry. Other combinations of acids and cleaners are useful as well and are selected depending upon the metal surface and composition of the desired mineral layer. Once the surface is pretreated, the surface can then be subjected to further activation, if necessary, to enhance the buffering capability, including but not limited to oxidation by any suitable method. Examples of suitable methods comprise immersion in hydrogen peroxide, sodium peroxide, potassium permanganate, mixtures thereof, among other oxidizers.

Depending upon the carrier and process condition, precursors can pass through the carrier membrane system as anions, and interact adjacent to or upon the surface with metal cations, which in most cases are donated by the metal surface or substrate to form a relatively thin mineralized layer, e.g., a monolayer. In one aspect of the invention, sodium silicate (as SiO3-ion) reacts with a zinc containing surface, e.g., that exists primarily as zinc carbonate, to form an amorphous mineralization layer containing a nanocrystaline hemimorphite phase that is normally less than 100 Angstroms in thickness. In this aspect of the invention, the metal surface was prepared for mineralization by the presence of a suitable buffering alkali, e.g., buffering with a silicate to a pH in the range of about 9.5 to about 10.5. While a higher pH can be effectively used, a pH of less than about 11 minimizes the need for certain relatively complex and expensive handling procedures.

In another aspect of the invention, the delivery of pH buffering agents as well as the anion reactants can be designed to tailor the surface characteristic. For example, in order to achieve improved resistance to acid rain on a zinc surface, the silicate anions can be complemented with zirconate anions. Further, in the case of an iron containing surface, the carrier can deliver silicate anions to a anodically conditioned surface to form amorphous phase comprising julgoldite.

In yet another aspect of the invention, a surface pretreament was used to enhance the mineralization layer formation. For example, in order to achieve an improved corrosion surface on iron, the steel substrate was first treated with a phosphoric acid containing cleaner, then exposed to an oxidizer in order to remove unwanted material and convert at least a portion of the surface to a homogeneous species of iron oxide. The mineralized layer was then formed on the pretreated metal surface by being contacted with sodium silicate containing precursor which in turn can proceed to form a clinopyroxene of sodium iron silicate. While any suitable buffer can be employed for practicing the invention, buffer solutions are typically prepared by mixing a weak acid and its salt or a weak base and its salt. Acidic buffers, for example, can be prepared using potassium chloride or potassium hydrogen phthalate with hydrochloric acid of appropriate concentrations. Neutral buffers can be prepared by mixing potassium dihydrogen phosphate and sodium hydroxide, for example. Alkaline (basic) buffers can be prepared by mixing borax or disodium hydrogen phosphate with sodium hydroxide, for example. Many more chemical combinations are possible, using appropriate chemicals to establish the proper sequence of proton transfer steps coupled with the intended reactions. Buffer exchange rates may be modified by combinations of buffer materials that react at different ionic exchange rates; buffers of low-change type react more rapidly than high-change types.

Aqueous polymers are preferred carriers for buffers in liquid form and include water reducible alkyds and modified alkyds, acrylic latexes, acrylic epoxy hybrids, water reducible epoxies, polyurethane dispersions, vinyls and ethylene vinyl acetates, and mixtures thereof. Such polymers are water vapor permeable but are repellent of liquid water and are essentially water insoluble after curing. These polymers can form a semipermeable membrane for water vapor and ionic transfer. Hence, if the surface of the metal substrate is dry, water vapor can permeate the membrane; but, buffering ions, which are present in the membrane or that pass through the membrane, can passivate the metal surface thereby reducing corrosion.

Buffer materials are chosen based on the type of the surface or substrate to be protected. Metal substrates may be protected from corrosion by passivating the substrate surface. Such passivation may generally be accomplished only in certain pH ranges which, in turn, depend on the specific substrate to be protected. For example, iron based alloys are passivated with an alkaline pH (pH 8-12). This pH range is preferably accomplished with sodium silicate and/or potassium silicate powders; but other alkaline materials may be used. A blend of sodium and potassium silicates is also useful for achieving viscosity control in aqueous carrier/membrane formulations.

In a further aspect of the invention, a mineralized layer is obtained by mixing silicates and anodic oxidizing materials such as sodium carbonate and delivering the mixture in a manner effective to activate the metal surface.

While the above description emphasizes a zinc containing surface, the surface of a wide range of metal surfaces can be altered to impart beneficial surface characteristics. In most cases, the substrate or the surface thereof contributes cations to the mineralization-forming reaction. Examples of metal surfaces include zinc, iron, copper, brass, iron, steel, stainless steel, lead, alloys thereof, among others. In the case of limited mineral layer formation or thickness of the mineral layer is caused by the surface contribution of the cation, an improved result can be obtained by managing or tailoring the pH. That is, the buffering capacity and the pH of the carrier is substrate surface-specific and is tailored to manage the surface chemistry to form the inventive mineralization layer, e.g., selecting a pH at which the surface is reactive encourages formation of the mineralization layer. The reaction for forming the new surface with continue until such time that the finite quantity of metal atoms at the surface are consumed. If the new mineralized layer is marred or destroyed, a desirable aspect of the instant invention is that the surface will reinitiate mineralization formation with any available precursors. The ability to reinitiate mineralization or self-repair damaged surfaces is a novel and particularly desirable characteristic of the invention.

The delivery/method of the alkali metal polyoxolates (or mineralization layer) can be provided through a membrane from a reservoir as described in the U.S. patent application Ser. No. 08/634,215; previously incorporated by reference. In the present invention, soluble precursors, such as silicate materials, are used within one or more coating layers. For example, in a polymer containing carrier system, one of the layers would be charged with sodium or potassium silicates wherein the outer layer(s) are employed to control the rate of moisture flow through the carrier. These carriers are typically relatively hard films as the normal polymerization of the carrier occurs to form a plastic type polymer type coating. Additional delivery methods have been developed utilizing soft films, gels, sealants, adhesives, and paints wherein the membrane feature is formed in-situ by the reaction between a silicate, e.g., sodium silicate, and silica. By controlling the quantity of the silica in the carrier, the mineralized layer can be designed to suit the specific application. Depending upon the pH and relative concentration of silicate and silica, the degree of crystal formation, e.g., a silica containing hemimorphite within an amorphous layer, can also be designed to achieve a predetermined result.

Without wishing to be bound by any theory or explanation the formation of the mineralized layer can occur under a wide range of conditions (normally ambient) and via a plurality of mechanisms. Normally, the mineralization layer forms underneath the carrier upon the metal surface, e.g., as buried layer under a carrier comprising a reservoir of precursors. If so formed, whatever ions are needed in the reservoir layer to form the mineralized layer, are expediently included as water soluble salts in the reservoir layer. On the other hand, all the ions employed to form the mineralized layer need not necessarily be included in the reservoir layer. That is, if desired cations can be supplied from the underlying metal surface and need not necessarily be included as water soluble salts in the reservoir layer. Such cations can be obtained from the surface of the substrate metal itself, by reaction of the substrate with the anions of the precursor component for the mineralized layer. Since the mineralized layer is normally relatively thin, sufficient cations for the mineralized layer can even be supplied from the substrate when present only as an alloying ingredient, or perhaps even as an impurity. Additionally, the cations needed for the mineralized layer can be supplied from water soluble salts in the reservoir layer, as indicated above. Further, if the mineralized layer is to be formed from an overlying reservoir layer that also contains buffer components, at least some to the salts used for buffering can be employed for forming the mineralized layer. The latter reservoir layer would possess a self healing effect by functioning as a source of minerization precursors in the event the layer was damaged. Once the mineralization layer has been formed to the degree desired, the carrier or reservoir layer can remain as a component of the finished article or removed.

In one embodiment of the invention, silicon can provide the predominate lattice-forming unit, e.g., CRN. The fundamental unit on which the structure of all silicates is based on consists of four O²⁻ at the apices of a regular tetrahedron surrounding and coordinated by one Si⁴⁺ at the center. A bond between silicon and oxygen atoms may be estimated by use of Pauling's electronegativity concept as 50% ionic and 50% covalent. That is, although the bond typically arises in part from the attraction of oppositely charged ions, the silicon-oxygen bond also involves sharing of electrons and interpretation of the electronic clouds of the ions involved. Each O²⁻ has the potential of bonding to another silicon atom and entering into another tetrahedral grouping, thus uniting the tetrahedral groups through the shared (or bridging) oxygen. Such linking of tetrahedra is often referred to as polymerization. In the case of silicate polymerization, the amount of oxygen is normally less that the stoicheometric amount of 4:1, Si:O. Silicates in which two SiO₄ groups are linked can produce Si₂ O₇ groups which are classed as disilicates. If more than two tetrahedra are linked, a closed ring like structure can be formed of a general composition Si_(x) O_(3x). Fourfold tetrahedral rings have composition Si₄ O₁₂. Tetrahedra may also be joined to form infinite single chains, called pyroxenes with a unit composition of SiO₃. Infinite double chains, classified as amphibles, normally possess a ratio of Si:O=4:11. Infinitely extending flat sheets are formed of unit composition Si₂ O₅. Three dimensional framework silicates, such as feldspars or zeolites, typically result in a network oxide of unit composition SiO₂.

In the present invention, silicates can be polymerized into a wide range of Si:O ratios. In the case of a zinc containing surface, the surface can interact with a mineral layer precursor to form a disilicate. In the case of an iron containing surface, the surface can interact with a suitable mineral layer precursor to form a chain silicate, e.g., a clinoperoxine. When silicate polymerization occurs in the instant invention, the covalency of the silicon-oxygen bond is decreased. This is evidenced by an increased binding energy of the photoelecton as detected by x-ray photoelectron spectrospopy, e.g., a binding energy between 102.0 to 103.3 eV in comparison to 101.5 eV for orthosilicate.

Without wishing to be bound by any theory of explanation it is also believed that the aforementioned inventive mineralized layer can comprise a complex oxide of the form:

MxyOt, wherein "M" represents one or more cationic elements having a covalency factor of less than about 0.5 that functions to balance the charge of the complex oxide, "N" represents one or more lattice forming elements having a covalency factor greater than about 0.15 that functions as the structural component of the complex oxide and optionally wherein the NyOt carries single or multiple crystal structures; and wherein x, y and t comprise any number the total of which balances the charge of the complex oxide. In some cases, the covalency factor of M is less than about 0.33 and the covalency factor N is greater than about 0.33.

Applications for the films and coatings of the invention include, for example, components such as coatings and paints of components, parts and panels for use the automotive industry, home-consumer products, construction and infrastructures, aerospace industry, and other out-door or corrosive applications wherein it is desirable to improve the characteristics of a metal surface and the use of heavy metals in elemental or non-elemental form is environmentally undesirable. The films and coatings may be applied to new products or over conventional platings to extend the useful service life of the plated component.

While the above description places particular emphasis upon forming a silicate containing mineralized layer, one or more mineralized layers having chemically similar or distinct compositions can be applied upon the same metal surface. If desired, the mineralized surface can be farther modified by using conventional physical or chemical treatment methods.

The following Examples are provided to illustrate not limit the scope of the invention as defined in the appended claims. These Examples contain results of the following analysis: Auger Electron Spectroscopy (AES), Electronic Impedance Spectroscopy (EIS), and X-ray Photoelectron Spectroscopy (XPS). These analysis were performed using conventional testing procedures. The results of the AES demonstrate that the thickness of the mineralized layer can range from about 10 to 50 microns. EIS demonstrates that the mineralized layer imparts corrosion resistant properties to the surface, e.g., a reduced Icorr corresponds to a reduced corrosion current and in turn a reduced corrosion rate. The XPS data demonstrates the presence of a unique hemimorphite crystal within the mineralized layer, e.g., XPS measures the bond energy between silicon and oxygen atoms and compares the measured energy to standardized values in order to determine whether or not known crystals are present. Conventional X-ray diffraction analysis confirmed that the mineralized layer is predominately amorphous, e.g., an X-ray measurement resulted in wide bands thereby indicating the presence of an amorphous phase.

EXAMPLES Auger Electron Spectroscopy

Examples 1-4 were prepared and analyzed in accordance with the following AES procedure.

    ______________________________________                                         Instrumentation Used                                                           ______________________________________                                         Instrument:      Physical Electronics 545, Single Pass                                          Cylindrical Analyzer                                          Sample Excitation:                                                                              Electron Gun                                                                   Emission Current, 1 mA                                                         Beam Voltage, 3 kV                                            Electron Beam Detection:                                                                        Multiplier Voltage, 1 kV                                                       Modulation Voltage, 3 eV                                      Signal Detection:                                                                               Lock-in Magnification, 10X                                                     Lock-in Time Constant, 0.001 sec.                             Sputter Gun Settings:                                                                           Beam Voltage, 3kV                                                              Focus Dial Setting, 2                                                          Raster X Dial Setting, 10                                                      Raster Y Dial Setting, 10                                                      Emission Current, 15, mA                                                       Sputter Rate, 12 Å/min                                                     Start Time, 0 min.                                                             Final Time, 30 min                                                             Sputter Depth, 360 Å                                      ______________________________________                                    

Example 1

The coating had a first layer with the following formulation (by weight): 25% Water (Fisher Scientific)

75% NeoRezR-9637 (Zeneca Resins)

and a second layer with the following formulation (by weight):

6.5% N-grade Sodium Silicate

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The components were mixed by hand for approximately 15 minutes. The first layer was then cast onto a standard 1010 steel test panel, obtained through ACT Laboratories, with a dry film thickness of about 0.5 to 0.7 mil. This layer was dried to tack free at 60 C for 10 minutes. The second layer was then applied, with a dry film thickness of about 0.5 to 0.7 mil. This layer was also dried to tack free at 60 C for 10 minutes. The second layer was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual coating was washed off with copious amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 2

The coating had one layer with the following formulation (by weight):

25% Water (Fisher Scientific)

75% NeoRezR-9637 (Zeneca Resins)

and a second layer with the following formulation (by weight)

6.5% N-grade Sodium Silicate

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The components were mixed by hand for approximately 15 minutes. The first layer was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, with a dry film thickness of about 0.5 to 0.7 mil. This layer was dried to tack free at 60 C for 10 minutes. The second layer was then applied, with a dry film thickness of about 0.5 to 0.7 mil. This layer was also dried to tack free at 60 C for 10 minutes. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual coating was washed off with copious amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 3

The coating had one layer with the following formulation (by weight):

25% Water (Fisher Scientific)

75% NeoRezR-9637 (Zeneca Resins)

and a second layer with the following formulation (by weight)

6.5% N-grade Sodium Silicate

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The components were mixed by hand for approximately 15 minutes. The first layer was then cast onto a standard zinc phosphated, 1010 steel test panel, obtained through ACT Laboratories, with a dry film thickness of about 0.5 to 0.7 mil. This layer was dried to tack free at 60 C for 10 minutes. The second layer was then applied, with a dry film thickness of about 0.5 to 0.7 mil. This layer was also dried to tack free at 60 C for 10 minutes. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copious amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 4

The coating had one layer with the following formulation (by weight):

25% Water (Fisher Scientific)

75% NeoRezR-9637 (Zeneca Resins)

and a second layer with the following formulation (by weight)

6.5% N-grade Sodium Silicate

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The components were mixed by hand for approximately 15 minutes. The first layer was then cast onto a standard iron phosphated, 1010 steel test panel, obtained through ACT Laboratories, with a dry film thickness of about 0.5 to 0.7 mil. This layer was dried to tack free at 60 C for 10 minutes. The second layer was then applied, with a dry film thickness of about 0.5 to 0.7 mil. This layer was also dried to tack free at 60 C for 10 minutes. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Each of the previously described washed test panels were passed through an AES analysis in accordance with conventional methods. This analysis confirmed the presence of the inventive mineral layer and generated data which demonstrated that for each substrate, the thickness of the mineralized layer was on the order of about 50 to about 70 Å thick.

Electrical Impedance Spectroscopy

Examples 5 through 13 were prepared for Electrochemical Impedance Spectroscopy (EIS) analysis. EIS is one method of determining corrosion rates of a metal or a coated metal. In this technique, a small-amplitude sinusoidal potential perturbation was applied to the working electrode at a number of discrete frequencies ranging from 60,000 Hz to 0.0005 Hz. At each one of these frequencies, the resulting current waveform exhibited a sinusoidal response that was out of phase with the applied potential signal by a certain amount. The electrochemical impedance was a frequency-dependent proportionality factor that acts as a transfer function by establishing a relationship between the excitation voltage signal and the current response of the system. This method was detailed by the American Society for Testing and Materials (ASTM) in Electrochemical Corrosion Testing, STP 727.

Example 5

A gel was prepared having the following formulation (by weight):

10% Cab-O-Sil TS-720 Silica

90% Amoco DURASYN™ 174 polyalphaolefin

The above formulation was mixed in a Hobart Mixer (model N-50) for approximately 30 minutes. The gel was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, at a thickness of 1/16" to 1/8". The gel was left on the panel for a minimum of 24 hours. Most of the gel was then removed with a plastic spatula. The residual gel was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 6

A gel was prepared having the following formulation (by weight):

10% Cab-O-Sil TS-720 Silica

20% G-Grade Sodium Silicate (PQ Corporation)

70% Amoco DURASYN™ 174 polyalphaolefin

The above formulation was mixed in a Hobart Mixer (model N-50) for approximately 30 minutes. The gel was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, at a thickness of 1/16" to 1/8". The gel was left on the panel for a minimum of 24 hours. Most of the gel was then removed with a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 7

A gel was prepared having the following formulation (by weight):

10% Cab-O-Sil TS-720 Silica

20% Sodium Molybdate (Fisher Scientific)

70% Amoco DURASYN™ 174 polyalphaolefin

The above formulation was mixed in a Hobart Mixer (model N-50) for approximately 30 minutes. The gel was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, at a thickness of 1/16" to 1/8". The gel was left on the panel for a minimum of 24 hours. Most of the gel was then removed with a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 8

A gel was prepared having the following formulation (by weight):

10% Cab-O-Sil TS-720 Silica

20% Sodium Phosphate (fisher Scientific)

70% Amoco DURASYN™ 174 polyalphaolefin

The above formulation was mixed in a Hobart Mixer (model N-50) for approximately 30 minutes. The gel was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, at a thickness of 1/16" to 1/8". The gel was left on the panel for a minimum of 24 hours. Most of the gel was then removed with a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

This Example was repeated with the exception that sodium carbonate was employed instead of sodium phosphate.

Example 9

A coating was prepared having the following formulation (by weight):

25% Water (Fisher Scientific)

75% NeoRezR-9637 (Zeneca Resins)

The above formulation was mixed by hand for approximately 15 minutes. The coating was then cast onto a standard 1010 steel test panel, obtained through ACT Laboratories, at a thickness for a total dry film thickness of 2.1 to 2.5 mils in three layers. Each layer was dried to tack free at 60 C for 15 minutes. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 10

A coating was prepared having the following formulation (by weight):

6.5% N-grade Sodium Silicate

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The above formulation was mixed by hand for approximately 15 minutes. The coating was then cast onto a standard 1010 steel test panel, obtained through ACT Laboratories, at a thickness for a total dry film thickness of 2.1 to 2.5 mils in three layers. Each layer was dried to tack free at 60 C for 15 minutes. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 11

A coating was prepared having the following formulation (by weight):

6.5% Sodium Vanadate Solution (156.3 gramns/liter)

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The above formulation was mixed by hand for approximately 15 minutes. The coating was then cast onto a standard 1010 steel test panel, obtained through ACT Laboratories, at a thickness for a total dry film thickness of 2.1 to 2.5 mils in three layers. Each layer was dried to tack free at 60 C for 15 minutes. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 12

A coating was prepared having the following formulation (by weight):

6.5% Sodium Molybdate Solution (274.21 grams/liter)

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The above formulation was mixed by hand for approximately 15 minutes. The coating was then cast onto a standard 1010 steel test panel, obtained through ACT Laboratories, at a thickness for a total dry film thickness of 2.1 to 2.5 mils in three layers. Each coat was dried to tack free at 60 C for 15 minutes. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 13

A coating was prepared having the following formulation (by weight):

6.5% Sodium Carbonate Solution (120.12 grams/liter)

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The above formulation was mixed by hand for approximately 15 minutes. The coating was then cast onto a standard 1010 steel test panel, obtained through ACT Laboratories, at a thickness for a total dry film thickness of 2.1 to 2.5 mils in three layers. Each layer was dried to tack free at 60 C for 15 minutes. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

The cleaned samples from Examples 5 to 13 were then tested by EIS in accordance with the following method.

    ______________________________________                                         Instrument:                                                                             Solartron 1287 Electrochemical Interface                                       Solartron 1260 Impedance/Gain-Phase Analyzer                                   ZWare and CorrWarr Software by Scribner                               Settings:                                                                               60,000 to .005 Hz.                                                             10 steps/decade                                                                5 mV rms AC signal                                                    Test Solution:                                                                          1Molar Ammonium Sulfate, pH = 3.0 (using 0.1 N                                 Sulfuric Acid) for electrogalvanized substrates.                               1Molar Ammonium Sulfate, pH = 2.0 (using 0.1 N                                 Sulfuric Acid) for 1010 Steel substrates.                             B value: corresponds to the average of the Tafel slope                                  B = (BcBa)/(Bc + Ba)                                                  i.sub.corr :                                                                            corresponds to the current generated by corrosion                     ______________________________________                                    

The following Table sets forth the results of the EIS Procedure for the zinc substrate in Examples 5-8.

    __________________________________________________________________________     EIS TABLE FOR ZINC SUBSTRATES                                                  __________________________________________________________________________                  i.sub.corr ave. i.sub.corr                                                                    EXPL                                               surface                                                                             B       μA/cm.sup.2                                                                     ave. B μA/cm.sup.2                                                                     NO.   Comments                                     __________________________________________________________________________     Bare Zinc                                                                           0.062632                                                                               193.3                                                                              0.067255                                                                              205.5                                                                              standard                                                0.060229                                                                               204.4          std                                                     0.063586                                                                               226.3          std                                                     0.101038                                                                                85.3          std   .sup.1                                            0.071548                                                                               213.1          std                                                      0.0792307                                                                             243.6          std   .sup.11                                           0.078282                                                                               190.2          std                                                Gel  0.054997                                                                               120.4                                                                              0.055658                                                                              130.1                                                                              5                                                       0.045513                                                                               148.5          5                                                       0.035642                                                                                64.8          5                                                       0.041034                                                                                79.7          5                                                       0.039146                                                                                72.5          5                                                       0.060190                                                                               113.1          5                                                       0.061932                                                                               138.5          5                                                  Na.sub.2 SiO.sub.4                                                                  0.072070                                                                               110.7                                                                              0.047529                                                                              97.5                                                                               6                                                       0.059899                                                                               121.5          6                                                       0.035932                                                                                93.2          6                                                       0.038235                                                                               107.7          6                                                       0.040076                                                                                67.3          6                                                       0.038964                                                                                84.7          6                                                  __________________________________________________________________________          B       i.sub.corr                                                                         ave. B ave. i.sub.corr                                                                    EXMPL                                              surface                                                                             (mV)    μA/cm.sup.2                                                                     (mV)   μA/cm.sup.2                                                                     NO    Comments                                     __________________________________________________________________________     Na.sub.2 MoO.sub.4                                                                  0.052667                                                                                99.3                                                                              0.061923                                                                              128.5                                                                              7                                                       0.072482                                                                               191.1          7                                                       0.059900                                                                                98.5          7                                                       0.065942                                                                               128.6          7                                                       0.058622                                                                               125.0          7                                                       0.090991                                                                               153.9          7     .sup.2                                       Na.sub.2 PO.sub.4                                                                   0.047173                                                                                93.3                                                                              0.049479                                                                              153.9                                                                              8                                                       0.045828                                                                               141.0          8                                                       0.053326                                                                               232.8          8                                                       0.056754                                                                               178.1          8                                                       0.058574                                                                               194.0          8                                                       0.035220                                                                                84.2          8                                                  Na.sub.2 CO.sub.3                                                                   0.041397                                                                                68.4                                                                              0.047339                                                                               98.7                                                                              8                                                       0.044320                                                                               121.8          8     .sup.2                                            0.046295                                                                                81.1          8                                                       0.057343                                                                               123.4          8     .sup.3                                       __________________________________________________________________________      .sup.1 Cell leaked at the base, setting up a localized galvanic cell.          .sup.1 Cell leaked underneath gasket.                                          .sup.2 Cell leaked at the base, discarded this data point.               

The results of the EIS indicates that the greatest corrosion resistance (low icorr) for a zinc substrate is obtained by a sodium silicate or sodium carbonate mineral layers.

The following Tables list the corrosion data for the steel surfaces of Examples 9-13.

    ______________________________________                                                    Hours    B       R.sub.p                                                                               i.sub.corr                                  surface    Immersed (mV)    (ohm-cm.sup.2)                                                                        (μA/cm.sup.2)                            ______________________________________                                         Coating Without Silicates - Example 9                                          steel      24       39.4    68     580                                         --         49       33.8    55     614                                         --         74       33.8    116     290, pH = 2.86                             --         99       33.8    25     1352, pH = 2.0                              --         21       34.4    54     637                                         --         44       36.3    95.8   379                                         --         68       45      55.6    808, pH = 2.36                             --         1        46.1    59.3   777                                         --         24       41.7    43.8   952                                         --         48       43.3    55.5    780, pH = 2.4                              --         1        42      135    311                                         --         24.5     40.8    51.8   788                                         --         48       40.5    53      764, pH = 2.5                              Coating Containing Sodium Silicate - Example 10                                steel      24       30.3    47.5   640                                         --         49       35.3    55     642                                         --         74       35.3    267     132, pH = 3.15                             --         99       35.3    20     1765, pH = 2                                --         1.5      43.4    74.4   584                                         --         21       35.5    94.2   377                                         --         44       31.5    125    252                                         --         68       33.8    172     196, pH = 2.25                             steel - coating                                                                           1        36.7    564     65                                         was not completely                                                             stripped                                                                       steel      26       33.2    371     90                                         --         57       33.2    554     60                                         steel - coating                                                                           1        42.4    32.6   1300                                        was restripped                                                                 steel      1        42.2    59.7   707                                         --         24       40.8    58.7   695                                         --         48       40.8    70.2    581, pH = 2                                Coating Containing Sodium Vandate - Example 11                                 steel      25       305.8   55.5   645                                         --         49       33.9    75.8   448                                         --         74       33.9    82.6   410, pH = 2.8                               --         78       42.2    25.7   1640, pH = 2                                --         1.5      50.5    70     721                                         --         21       36.5    92     397                                         --         44       33.3    126    265                                         --         68       33.2    161     206, pH = 2.25                             --         1        40.8    146    280                                         --         24       40.6    64.6   632                                         --         48       40.6    75.6    537, pH = 2                                --         1        42.6    62.9   677                                         --         24       34.6    65     536                                         --         48       39.1    110    355, pH = 2.1                               Coating Containing Sodium Molybdate - Example 12                               steel      21       37.4    51.3   729                                         --         44       44.4    45.6   973                                         --         68       41.4    54.3    763, pH = 2.35                             steel - coating                                                                           1        37.7    190    198                                         was not completely                                                             removed                                                                        steel      26       36.6    138    265                                         --         57       36.6    212    173                                         steel - coating                                                                           1        33.3    112    353                                         was not completely                                                             removed)                                                                       --         24       40.4    96.6   409                                         --         48       39.5    130    293, pH = 2.2                               --         1        46.9    42.5   1109                                        --         24       48.2    28.6   1687                                        --         44       46      45.2   1018, pH = 2.15                             Coating Containing Sodium Carbonate - Example 13                               steel      25       37.2    82.5   451                                         --         49       27.6    123.5  223                                         --         74       27.6    128.8  214, pH = 2.3                               --         78       37.2    34.4   1080, pH = 2                                --         1        41.8    56.8   735                                         --         24.5     44.2    33.5   1320                                        --         48       43.4    40.7   1066, pH = 2.9                              --         1        39.5    112    353                                         --         24       40.6    96.6   409                                         --         48       38.1    130    293, pH = 2.2                               --         1        45.7    46.7   978                                         --         24       46.5    29.7   1566                                        --         44       44.4    41.4   1072  pH = 2.15                             ______________________________________                                    

Base upon the measured corrosion currents, sodium carbonate and sodium silicate are the most effective in reducing the icorr thereby indicating a reduced corrosion rate.

X-Ray Photoelectron Spectroscopy (XPS)

X-ray Photoelectron Spectroscopy (XPS) was performed on a series of samples in Examples 14-24 that included 1010 Steel and Electrogalvanized Steel. XPS was performed in accordance with conventional procedures in this art.

    ______________________________________                                         Instrumentation Used                                                           ______________________________________                                         Instrument:      Physical Electronics 5701 LSci                                X-ray Source:    Monochromatic aluminum                                        Source Power:    350 watts                                                     Analysis Region: 2 mm × 0.8 mm                                           Exit angle:      65°                                                    Acceptance angle:                                                                               ±7°                                                 Charge reference:                                                                               B.E. of C-)H,C) = 284.6 eV                                    Charge neutralization:                                                                          flood gun                                                     Sampling Depth:  (3) was 70 Å                                              ______________________________________                                    

Example 14

A coating was prepared having the following formulation (by weight):

25% Water (Fisher Scientific)

75% NeoRezR-9637 (Zeneca Resins)

The above formulation was mixed by hand for approximately 15 minutes. The coating was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, for a total dry film thickness of 2.1 to 2.5 mils in three layers. Each layer was dried to tack free at 60 C for 15 minutes. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 15

A coating was prepared having the following formulation (by weight):

25% Water (Fisher Scientific)

75% NeoRezR-9637 (Zeneca Resins)

The above formulation was mixed by hand for approximately 15 minutes. The coating was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, for a total dry film thickness of 2.1 to 2.5 mils in three layers. Each layer was dried to tack free at 60 C for 15 minutes. The coated panel was then exposed to a post-cure heat treatment of 1 hour at 125° C., using a standard laboratory oven. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 16

A coating was prepared having the following formulation (by weight):

6.5% N-grade Sodium Silicate

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The above formulation was mixed by hand for approximately 15 minutes. The coating was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, for a total dry film thickness of 2.1 to 2.5 mils in three layers. Each layer was dried to tack free at 60 C for 15 minutes. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 17

A coating was prepared having the following formulation (by weight):

6.5% N-grade Sodium Silicate

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The above formulation was mixed by hand for approximately 15 minutes. The coating was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, for a total dry film thickness of 2.1 to 2.5 mils in three layers. Each layer was dried to tack free at 60 C for 15 minutes. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 18

A coating was prepared having the following formulation (by weight):

6.5% N-grade Sodium Silicate

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The above formulation was mixed by band for approximately 15 minutes. The coating was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, for a total dry film thickness of 2.1 to 2.5 mils in three layers. Each layer was dried to tack free at 60 C for 15 minutes. The coated panel was then exposed to a post-cure heat treatment of 125° C. for one hour, in a standard laboratory oven. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 19

A coating was prepared having the following formulation (by weight):

6.5% N-grade Sodium Silicate

13% Water (Fisher Scientific)

80.5% NeoRezR-9637 (Zeneca Resins)

The above formulation was mixed by hand for approximately 15 minutes. The coating was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, for a total dry film thickness of 2.1 to 2.5 mils in three layers. Each layer was dried to tack free at 60 C for 15 minutes. The coated panel was then exposed to a post-cure heat treatment of 175° C. for one hour, in a standard laboratory oven. The coating was left on the panel for a minimum of 24 hours. Most of the coating was then removed with BIX Stripper (Walmart Stores) and a plastic spatula. The residual was washed off with copius amounts of Naptha (Commercial Grade, Walmart Stores), and Reagent Alcohol (Fisher Scientific).

Example 20

For purposes of comparing the results achieved by Examples 14-19, an electrogalvanized panel was soaked for 24 hours in a solution that had the following formulation (by weight):

25 mg/l Sodium Silicate

The sample panel was allowed to air dry.

Example 21

For purposes of comparing the results achieved by Examples 14-19, an electrogalvanized panel was soaked for 24 hours in a solution that had the following formulation (by weight):

25 mg/l Sodium Silicate

The sample panel was allowed to air dry. The panel was then exposed to a post-dry heat treatment of 125° C. for one hour, in a standard laboratory oven.

Example 22

For purposes of comparing the results achieved by Examples 14-19, an electrogalvanized panel was soaked for 24 hours in a solution that had the following formulation (by weight):

25 mg/l Silicate

The sample was allowed to air dry. The panel was then exposed to a post-dry heat treatment of 125° C. for one hour, in a standard laboratory oven.

Example 23

A crystal sample of Zn₂ SiO₄, which was air fractured and immediately introduced into the sample chamber of the XPS. The total air exposure was less than 2 minutes. The surface was examined initially with a low resolution survey scan to determine which elements were present. High resolution XPS spectra were taken to determine the binding energy of the elements detected in the survey scan. The quantification of the elements was accomplished by using the atomic sensitivity factors for a Physical Electronics 5701 LSci ESCA spectrometer.

The following Table sets forth the silicon binding energies which were measured for Examples 14-23.

    ______________________________________                                         Example Number                                                                              Treatment   Si 2p peak Energy (eV)                                ______________________________________                                         14           RoomTemp    101.9                                                 15           125° C.                                                                             101.8                                                 16           Room Temp   102.8                                                 17           Room Temp   102.8                                                 18           125° C.                                                                             102.6                                                 19           175° C.                                                                             102.6                                                 20           25 ppm Na.sub.2 SiO.sub.4,                                                                 101.7                                                              25° C.                                                     21           25 ppm Na.sub.2 SiO.sub.4,                                                                 101.7                                                              125° C.                                                    22           25 ppm Na.sub.2 SiO.sub.4,                                                                 101.8                                                              175° C.                                                    23           Zn.sub.2 SiO.sub.4  crystal                                                                101.5                                                 ______________________________________                                    

The above Table illustrates that there has been a change in the concentration of Si as well as the bond energy thereby providing filter confirmation of the presence of the mineralized layer. Further, the Si--O bond energy of conventional zinc silicate crystal as well as the silicate soaked panels is distinct from the inventive mineralized layer.

Example 24

A coating was prepared having the following formulation (by weight):

6.5% grade Sodium Silicate

13% Water (Fisher Scientific)

80% NeoRezR-9637 (Zeneca Resins)

The formulation above was mixed by hand for approximately 15 minutes. The coating was then cast onto a standard electrogalvanized test panel, obtained through ACT Laboratories, for a total dry film thickness of 2.1 to 2.5 mils in three coats. Each coat was dried to tack free at 60 C for 15 minutes. The panel was exposed to ASTM B117 Salt Fog Chamber for 2400 hours. At the end of the salt fog exposure, there were large areas of the panel that were uncorroded. The area of uncorroded surface was cut into a small square sample and the urethane coating was removed by hand, using small tweezers. The sample was analyzed in accordance with the previously identified XPS method on an instrument of comparable sensitivity and accuracy. The results of the XPS are set forth in the following Table.

    ______________________________________                                         Example 24 Silicate Containing Coating Followed by Salt Spray Exposure                                        Relative Concentration                                                         of Silicon                                      Example              Si 2p peak                                                                               on the Surface                                  Number Treatment     Energy (eV)                                                                              (% wt)                                          ______________________________________                                         14     urethane coating, room                                                                       101.9     negligible at 1.0%                                     temp                                                                    15     urethane coating,                                                                            101.8     negligible at 0.8%                                     125° C.                                                          16     silicate, room temp                                                                          102.8     19.8%                                           17     silicate      102.8     18.9%                                                  125° C.                                                          18     silicate,     102.6     15.8%                                                  room temp                                                               19     silicate,     102.6     11.6%                                                  175° C. (heat applied                                                   after coating removed)                                                  20     immersion,    101.7     4.1%                                                   25 ppm Na.sub.2 SiO.sub.4,                                                     25° C.                                                           21     immersion,    101.7     3.2%                                                   25 ppm Na.sub.2 SiO.sub.4,                                                     125° C.                                                          22     immersion,    101.8     3.9%                                                   25 ppm Na.sub.2 SiO.sub.4,                                                     175° C.                                                          23     Zn.sub.2 SiO.sub.4  crystal                                                                  101.5     NA                                              24     silicate, room temp,                                                                         102.6     8.1%                                                   2400 hours of B117                                                             exposure                                                                ______________________________________                                    

The above Table illustrates that the binding energy for the surface exposed to the silicate containing coatings range from 102.6 to 102.8. By observation of the XPS peak, it was observed that these energy values were actually manifold values from manifold peaks that contain more than one material. These materials can be characterized as a disilicate, or hemimorphite (bonding energy at 102.2), altered by the presence of Si--O bonds, as in SiO2 (bonding energy at 103.3) and Si--O--C bonds with a bonding energy of 103.6 or 103.7. Such a bonding energy and concentration of Si on the surface are distinct from conventional silica or silicate structures. The binding energy, for zinc silicate, Zn₂ SiO₄, 101.5 eV, is also distinct from the binding energy of the mineralized layer, 102.7 eV, or the hemimorphite.

Example 25

This Example illustrates a process for pretreating a metal surface in order to enhance formation of the inventive silicate containing layer/surface.

1. Immerse panel in solution of 25% Metalprep 79 (Parker-Amchem) for 2 minutes,

2. Remove Panel and rinse with deionized water,

3. Scrub panel gently with "Kim-Wipe",

4. Rinse with deionized water and wipe off excess with Kim-wipe,

5. Immerse panel in 0.1 M NaOH solution for 10 sec.,

6. Wipe off excess with Kim-wipe,

7. Immerse panel in 50% H2O2 solution for 5 min.; and,

8. Wipe off excess with Kim-wipe.

Example 26

A cold rolled steel panel (ACT Labs) was prepared with the pretreatment process described in Example 25. The pretreated panel was then coated with a first layer comprising the following formulation (by wt %):

25% Water (Fisher Scientific); and,

75% NeoRezR-9637 (Zeneca Resins).

A second and third layer comprising the following formulation were then applied upon the first layer (by weight):

13% N-grade Sodium Silicate,

6.5% Water (Fisher Scientific); and,

80.5% NeoRezR-9637 (Zeneca Resins).

Each aforementioned formulation was mixed by hand for approximately 10 minutes. Each layer was applied at a 1.2 mil wet film thickness and cured for 15 minutes at 60 C to form for a tack-free finish. The panels were allowed to set overnight (or longer) and the coating was physically removed by hand.

XPS analysis was performed on the surface of this panel. The characteristic NaFe (SiO₃)₂ Si(2p) photoelectron binding energy was used to identify the species on the surface. The surface was characterized as a iron pyroxene species with the empincal formula of NaFe(SiO₃)2. Comparison of a clinopyroxene, a naturally occurring iron pyroxene, indicates that the species on the surface of the panel is indeed a matrix of a polymerized SiO₃ and iron.

Example 27

A electrozinc galvanized panel (ACT Labs) was prepared with the pretreatment method described above in Example 25. The panel was then coated with the following first formula (by wt %):

25% Water (Fisher Scientific); and,

75% NeoRezR-9637 (Zeneca Resins).

A second and third layer with the following formulation (by weight) were applied upon the first layer:

6.5% N-grade Sodium Silicate,

13% Water (Fisher Scientific); and,

80.5% NeoRezR-9637 (Zeneca Resins).

Each formula was mixed by hand for approximately 10 minutes. Each layer was applied at a 1.2 mil wet film thickness and given a 15 minute 60 C cure to allow for a tack-free finish. The panels were allowed to set for 1 hour and the coating was physically removed by hand.

Example 28

A electrozinc galvanized panel (ACT Labs) was prepared with the pretreatment method described in Example 25. The panel was then coated with two layers of the following formula (by wt %):

1.0% N-grade Sodium Silicate,

18.5% Water (Fisher Scientific); and,

80.5% NeoRezR-9637 (Zeneca Resins).

Each formula was mixed by hand for approximately 10 minutes. Each layer was applied at a 1.2 mil wet film thickness and given a 15 minute 60 C cure to allow for a tack-free finish. The panels were allowed to set for 24 hours and the coating was physically removed by hand.

The coated galvanized panels were recovered and analyzed in accordance with the previously described ESCA/XPS methods. XPS analysis was performed on both panels. A first panel shows the Si(2p) photoelectron binding energy of 102.1 eV representing a zinc disilicate species. A second panel also shows the same binding energy at 102.1 eV also indicating the presence of a zinc disilicate species on the surface of the zinc. The second test panel also has significantly more silica on the surface, represented by the 103.3 eV binding energy than does the first panel. Because of the accumulation of silica on the surface of panel #2, the relative amount of zinc decreases due to the limited sampling depth of XPS. The Zn:Si ratio goes down from 2.0 to 0.43 on panel #1 to panel #2, respectively, as would be expected when the build up of silica increases on the panel surface. In both cases, the formation of a zinc disilicate protective species was detected.

Example 29

Cold rolled steel panels (ACT Laboratories) were coated with the following formula (by wt %) to form a first layer:

25% Water (Fisher Scientific); and,

75% NeoRezR-9637 (Zeneca Resins).

A second layer with the following formulation (by wt%) was applied upon the first layer:

X% N-grade Sodium Silicate,

(19.5-X)% Water (Fisher Scientific); and,

80.5% NeoRezR-9637 (Zeneca Resins),

wherein X is a number, either 1.0 or 0.01 wt. %, as described below. A second layer with the same composition of the first layer was applied. Each formula was mixed by hand for approximately 10 minutes. Each layer was applied at a 1.2 mil wet film thickness and given a 15 minute 60 C cure to allow for a tack-free finish. Each panel was given a heat treatment for 1 hour at the temperature described in the table below. The panels were allowed to set overnight.

    ______________________________________                                         Panel Silicate conc         B2247 fail time                                                                         Adhesion                                  Set # (X %)     Heat temp (C.)                                                                             Humidity rating                                    ______________________________________                                         1     0.01      60          8        1                                         2     0.01      125         8        9                                         3     1.0       60          24       1                                         4     1.0       125         24       10                                        ______________________________________                                    

Two sets of tests were performed to examine the degree of protection against corrosion and the adhesion properties of the urethane coating to the steel surface. Corrosion protection was measured by time to reach 5% red rust coverage by humidity exposure according to ASTM B2247. Adhesion was measured by immersing the panels in deionized water for 10 minutes followed by 24 hour humidity exposure. The panel coatings were then scribed using a razor blade in a "X" pattern. Tape was placed over the scribe and pulled back. Performance was rated on a scale of 1-10, 1=no adhesion and complete removal of coating, 10=excellent adhesion, no removal of coating.

The results, illustrated in the table above, show that increased loadings of silicate in the urethane coating improve corrosion protection. For best results, the amount of mineral layer precursor or sodium silicate is greater than 0 and less than about 7 wt. %, normally about 0.1 to about 0.01 wt % silicate, and heat treated at a temperature of about 125 C.

It is to be understood that the foregoing is illustrative only and that other means and techniques may be employed without departing from the spirit or scope of the invention as defined in the following claims. 

The following is claimed:
 1. An amporphous mineralized coating upon an ion containing surface wherein the amorphous mineralized coating has a formula A_(x) B_(y) O_(z) -nH₂ O wherein A comprises iron and B comprises silicon, and the values of x, y and z are greater than zero;wherein the amorphous mineralized coating comprises an amorphous phase and inorganic complex oxide crystals.
 2. A corrosion resistant mineralized coating upon an iron containing surface wherin said coating has a formula A_(x) B_(y) O_(z) --n H_(z) O wherein A comprises iron and B comprises silicon and the values of x, y and z are greater than zero, and the coating comprises an amorphous phase and an inorganic complex oxide containing at least one member chosen from the group of codium, calcium and potassium.
 3. A corrosion resistant mineralized coating upon a metal containing surface wherein said coating has a formula A_(x) B_(y) O_(z) --n H₂ O wherein A comprises iron and B comprises silicon and the values of x, y and z are greater than zero, and the coating comprises an amorphous phase and an inorganic complex oxide.
 4. The amorphous mineralized coating of claim 1 or the corrosion resistant mineralized coating of claim 2 or 3 further comprising at least one dopant chosen from the group of aluminum tungsten, molybdenum, chromium, titanium , zirconium, vanadium, phosphorus, aluminum, boron, bismuth, galtium, tellurium, germanium, antimony, niobium, magesium and manganese.
 5. The amouphous mineralized coating upon a metal containing surface or the corrosion resistant mineralized coating claim 4 wherein the dopant comprises aluminum.
 6. The corrosion resistant mineralized coating of claim 2 wherein said at least one member comprises sodium.
 7. The amorphous mineralized coating of claim 1, or the corrosion resistant mineralized coating of claim 2 or 3 wherein the predominate phase of the coating comprises the amorphous phase.
 8. The corrosion resistant mineralized coating of claim 3 wherein said metal containing surface comprises iron. 